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United States Patent: 4684457


































 
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	United States Patent 
	4,684,457



 McKechnie
,   et al.

 
August 4, 1987




 Method for desalting crude oil



Abstract

The salt content of crude oil is reduced by washing it with at least 1% by
     volume of wash water of lower salinity than the water present in the crude
     oil and separating the resulting mixture of oil and water into a layer of
     crude oil of reduced salt content and a layer of saline water containing
     some oil. The latter is passed through a cross-flow membrane separator and
     the oil-free permeate is removed from the separator as effluent. The oil
     retentate is recycled from the separator to the washing stage and a
     quantity of lower salinity than the water associated initially with the
     crude oil is added to the washing stage. The quantity of added water
     corresponds at least to the volume of permeate removed from the cross-flow
     membrane separator.
Since the oil is recycled, the need for oil recovery plant for treating
     desalter effluent is removed.


 
Inventors: 
 McKechnie; Malcolm T. (Egham, GB2), Thompson; David G. (Richmond, GB2) 
 Assignee:


The British Petroleum Company p.l.c.
 (London, 
GB2)





Appl. No.:
                    
 06/806,474
  
Filed:
                      
  December 9, 1985


Foreign Application Priority Data   
 

Dec 20, 1984
[GB]
8432278



 



  
Current U.S. Class:
  208/188  ; 208/187; 210/799
  
Current International Class: 
  C10G 31/00&nbsp(20060101); C10G 31/08&nbsp(20060101); C10G 033/04&nbsp()
  
Field of Search: 
  
  


 208/188,187 210/799
  

References Cited  [Referenced By]
U.S. Patent Documents
 
 
 
3417013
December 1968
Roberts

3487927
January 1970
Yahnke

4551239
November 1985
Merchant



 Foreign Patent Documents
 
 
 
459489
Dec., 1970
SU



   Primary Examiner:  Konopka; P. E.


  Attorney, Agent or Firm: Morgan & Finnegan



Claims  

We claim:

1.  A method for reducing the salt content of crude oil which method comprises washing crude oil containing salt water with at least 1% by volume of wash water of lower salinity than the
water present in the crude oil, expressed as a percentage by volume of the crude oil, separating the resulting mixture of oil and water into a layer of crude oil of reduced salt content and a layer of saline water, passing the saline water through a
cross-flow membrane separator having a membrane surface, removing the permeate from the separator as effluent, recycling the retentate via a recycle stream from the separator to the washing stage, and adding to washing stage a quantity of water of lower
salinity than the water associated initially with the crude oil, the quantity of added water corresponding at least to the volume of permeate removed from the cross-flow membrane separator.


2.  A method according to claim 1 wherein the added water is added directly to the recycle stream.


3.  A method according to claim 1 wherein the amount of wash water employed is in the range 1 to 50% by volume of the crude oil.


4.  A method according to claim 1 wherein a demulsifier is added to the wash water before washing the crude oil.


5.  A method according to claim 4 wherein the demulsifier is water soluble.


6.  A method according to claim 4 wherein the concentration of the demulsifier is in the range 1 to 500 ppm.  Description  

This invention relates to a method for desalting crude petroleum in which
problems associated with subsequent effluent treatment are overcome.


Crude oil is generally found in a reservoir in association with salt water and gas.  The oil and gas occupy the upper part of the reservoir and below there may be a considerable volume of water, usually saline, which extends throughout the lower
levels of the rock.  As the reservoir becomes depleted, the oil/water interface in the reservoir rises and at some stage, water will be co-produced with the oil.


The mixture of water and oil is subjected to a high degree of turbulence as it flows through the well tubing and particularly as it passes through the well-head choke and other production facilities such as pumps.  These actions form an emulsion
in which water droplets are dispersed throughout the crude oil phase.  The presence of indigenous surfactants in the crude oil also stabilises the emulsion by forming a rigid interfacial layer which prevents the water droplets from contacting and
coalescing with one another.


Thus, following production, crude oil can contain dispersed water to a greater or lesser extent and this must be removed.  The action of water removal is termed crude oil dehydration.  Some emulsions may be broken down by heat alone but more
often it is necessary to add a surface tension reducing chemical to achieve this end.  Generally the application of heat and/or chemical is sufficient to reduce the water content, and more importantly the salt content, to an acceptable level but
sometimes it is necessary to use electrostatic precipitation.


A dehydrated oil normally contains between 0.1 and 1.0% by vol. of water.  However, if the salinity of the remaining water is high, the salt content of the crude oil will also be high, e.g. between 100-500 ptb (lbs salt per 1000 barrels of crude
oil), even when such low quantities of water are present.  This is undesirable because the presence of salt reduces the value of the crude oil, leads to the corrosion of pipelines and downstream distillation columns, fouling of heat exchangers and may
poison catalysts used in downstream refining processes.


With most crude oils it is necessary to remove the salt from the crude oil by washing with fresh water or a low salinity aqueous phase, imparting a degree of mixing to ensure adequate contact between high salinity water in the crude and low
salinity wash water and then carrying out the separation process by any of the means described above.  This process is termed crude oil desalting.


The two processes of dehydration and desalting may both be carried out at the production location to give a crude oil of export quality, typically with less than 1% water and 20 ptb salt.  Furthermore, an additional desalting process may be
carried out after the crude oil is received at a refinery.


Normally in desalting a small amount (1-10% vol/vol) of fresh water or water of low salinity is added to the dehydrated crude oil.  Adequate mixing of the wash water and crude oil to be desalted is required to induce good contact between saline
droplets, salt crystals, if present, dispersed wash water droplets and emulsifier, if added.  Consequently, an emulsion is produced which can be very stable with a low average droplet size.  For a given crude oil and mixing intensity, the less wash water
that is used, the lower the average droplet size and the more difficult the emulsion is to break.  Washing with relatively large quantities of water results in the formation of a less stable emulsion, and consequently, less severe conditions are required
for ultimate destabilisation (as disclosed in our copending European Patent Specification No. 0142278).


A problem associated with the use of relatively large quantities of fresh water or water of low salinity is its limited availability in many oil producing locations and at some refineries.  However, this problem can be reduced considerably by
recycling a portion of the separated wash water with some make-up.


Assuming optimum mixing, subsequent destabilisation of the emulsion can reduce the salt content to as low as 2 ptb (6 ppm).  In order to desalt to such low levels, however, it is necessary to use conditions of high temperature, a chemical
demulsifier and often electrostatic separation.  Demulsifiers usually comprise blends of surface active chemicals, e.g., ethoxylated phenolic resins, in a carrier solvent.


The saline water which is removed from the system contains a significant proportion of oil, however, and is not suitable for discharge without further treatment.


We have now discovered that passing the saline water from the settling stage through a cross-flow membrane separator results in a permeate of relatively oil-free salt water suitable for discharge and a retenate of salt water of enhanced oil
concentration.


The oily retentate or crossflow, is recycled to the washing stage and reinjected in the oil phase.  Thus removal of oil from the oily crossflow is unnecessary.  Providing the recycled water does not comprise more than 50% of the total wash water,
the salt content of the combined recycle plus make up water will attain a constant value and not increase continuously.


Thus according to the present invention, there is provided a method for reducing the salt content of crude oil which method comprises washing crude oil containing salt water with at least 1% by volume of wash water of lower salinity than the
water present in the crude oil (expressed as a percentage by volume of the crude oil), separating the resulting mixture of oil and water into a layer of crude oil of reduced salt content and a layer of saline water, passing the saline water through a
cross-flow membrane separator, removing the permeate from the separator as effluent, recycling the retentate from the separator to the washing stage, and adding to washing stage a quantity of water of lower salinity than the water associated initially
with the crude oil, the quantity of added water corresponding at least to the volume of permeate removed from the cross-flow membrane separator.


Preferably the added water is added directly to the recycle stream.


Cross-flow membrane separators are known and are described for example in The Chemical Engineer, June 1984, pages 10-14.  In essence, a cross-flow membrane separator comprises a membrane surface which can be in various configurations such as flat
sheets, pleated sheets, spiral wound or tubular and may incorporate means for promoting surface turbulence.  The liquid stream to be treated is passed into the membrane unit and introduced parallel to the surface of the membrane.  The component of the
flow which passes through the membrane material is termed filtrate or permeate and the second component which flows tangentially across the membrane surface is known as the retentate, non-permeate or cross-flow component.


Unlike conventional equipment for treating oily water, a cross-flow membrane separator does not itself remove or adsorb the oil, but allows it to return to the desalter.  This has the following advantages:


(a) Oil is not recovered from the membrane separator as oily slops and hence the need for oil recovery plant for treating desalter effluent, such as slop tanks is removed;


(b) The load on effluent treatment plant such as API separators is reduced as most of the oil is removed in a single stage by the cross-flow membrane separator;


Clean cross-flow membrane separators operate under conditions of high flux (e.g. 100 1/min/m.sup.2 membrane) and low pressure drop (e.g. 1-3 bar).


This may deteriorate in operation as a result of build-up of deposits on their surface but can easily be regenerated by a simple backwash procedure.


Preferably the amount of wash water employed to treat the crude oil is in the range 1% to 50% by volume of the crude oil.


Preferably a demulsifier is added to the wash water before washing the crude oil to assist in breaking the water/crude oil emulsion.


There are significant advantages to be gained by using a water soluble demulsifier, particularly when the chemical is added to the wash water, because it is then dispersed together with the lower volume component, i.e. wash water, and more
readily reaches the oil-water interface where the chemical is required to effect droplet coalescence.


To date, however, use of water soluble demulsifiers has been unattractive since they often give rise to stable, oily, separated water streams which require further treatment.  Since, according to the present invention, the oily water stream is
recycled, the problem of disposing of it does not arise.


If the demulsifier is water soluble, a large proportion will be recycled with the recycled oily water and only a top up will be required, thus reducing the chemical consumption.  Furthermore, the possibility of demulsifier poisoning refinery
catalysts is reduced when using a water-soluble as opposed to an oil-soluble demulsifier.


Suitable water soluble demulsifiers include silicone polyethers, petroleum sulphonates, ethylene oxide-propylene oxide block copolymers, polyglycol ethers and alkyl aryl ethoxylates, which are used with or without cosurfactants and/or solvents
according to conventional demulsifier technology.


Suitable demulsifier concentrations are in the range 1 to 500 ppm, preferably 2 to 50 ppm.


Desalting may be carried out in the presence or absence of an electric field at a temperature in the range ambient to 150.degree.  C. depending on the temperature of the oil.  At refineries, it is convenient to use desalters operating within the
temperature range 100.degree.-150.degree.  C . 

The invention is illustrated with reference to the accompanying drawing, which is a schematic drawing of a desalting process. 

Dehydrated crude oil (salt water content 0.2% by vol) is fed by
line 1 to a heat exchanger 2.  Wash water (5% vol/vol) containing a water soluble demulsifier is added through line 12 to the oil prior to heating.


The mixture of oil, salt water, wash water and demulsifier is passed through the heat exchanger 2, where its temperature is raised and then through line 3 and mixing valve 4 to a desalter 5.


Coalescence occurs in the desalter 5 and an aqueous layer containing some oil separates beneath the desalted crude oil which is taken off by line 6.


The aqueous layer is fed by line 7 to a flat-sheet cross-flow membrane separator 8 where 50% of the feed water permeates through the membrane and is discharged as relatively oil-free water through line 9.


The remaining 50% of the water containing the oil flows across the membrane surface and is recycled to the heat exchanger 2 by line 10.


The recycled oily wash water is joined by a make-up stream of fresh water 11 corresponding in quantity to that removed by line 9.


A water soluble demulsifier is added to the combined make-up and recycle line 12 by injector 13.


The invention is further illustrated with reference to the following Examples which describe the operation of the separator 8.


EXAMPLE 1


The filter was a nitrocellulose membrane with a pore rating of


1.2 .mu.m.  The cross-flow channels had a depth of 1 to 2 mm.  The water to be treated contained both oily and solid matter.


Operating conditions were as follows:


______________________________________ Temperature 25.degree.-30.degree. C.  Pressure differential  0.7 bar  Cross-flow stream 1 l/min  Area of membrane used for filtration  0.045 m.sup.2  Filtrate flux immediately before  2 l/min/m.sup.2 
regeneration  Operating period 2 hours  Regeneration procedure  backwash at 1.5 l/min  for 10 secs every 10 mins  ______________________________________


The results obtained are set out in the following Table.


EXAMPLE 2


The filter was a polyvinylidene fluoride membrane with a pore rating of 0.45 pm.


The filtrate flux immediately before regeneration was 1.5 1/min/pm.sup.2.  In other respects, conditions were as in Example 1.


EXAMPLE 3


The filter was a polycarbonate membrane with a pore rating of 0.2 .mu.m.


The filtrate flux immediately before regeneration was 1.4 1/min/m.sup.2.  In other respects, conditions were as in Example 1.


 TABLE  ______________________________________ Oil Content Solids Content  Feedstock Filtrate Feedstock  Filtrate  Example mg/l mg/l mg/l mg/l  ______________________________________ 1 70 16 19 1  2 160 21 10 1  3 120 19 28 5 
______________________________________


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DOCUMENT INFO
Description: This invention relates to a method for desalting crude petroleum in whichproblems associated with subsequent effluent treatment are overcome.Crude oil is generally found in a reservoir in association with salt water and gas. The oil and gas occupy the upper part of the reservoir and below there may be a considerable volume of water, usually saline, which extends throughout the lowerlevels of the rock. As the reservoir becomes depleted, the oil/water interface in the reservoir rises and at some stage, water will be co-produced with the oil.The mixture of water and oil is subjected to a high degree of turbulence as it flows through the well tubing and particularly as it passes through the well-head choke and other production facilities such as pumps. These actions form an emulsionin which water droplets are dispersed throughout the crude oil phase. The presence of indigenous surfactants in the crude oil also stabilises the emulsion by forming a rigid interfacial layer which prevents the water droplets from contacting andcoalescing with one another.Thus, following production, crude oil can contain dispersed water to a greater or lesser extent and this must be removed. The action of water removal is termed crude oil dehydration. Some emulsions may be broken down by heat alone but moreoften it is necessary to add a surface tension reducing chemical to achieve this end. Generally the application of heat and/or chemical is sufficient to reduce the water content, and more importantly the salt content, to an acceptable level butsometimes it is necessary to use electrostatic precipitation.A dehydrated oil normally contains between 0.1 and 1.0% by vol. of water. However, if the salinity of the remaining water is high, the salt content of the crude oil will also be high, e.g. between 100-500 ptb (lbs salt per 1000 barrels of crudeoil), even when such low quantities of water are present. This is undesirable because the presence of salt reduces the value of the crude oil